Chemical speciation of environmentally significant metals with inorganic ligands. Part 3: The Pb2+ + OH–, Cl–, CO32–, SO42–, and PO43– systems (IUPAC Technical Report)

Kipton J. Powell; Paul L. Brown; Robert H. Byrne; Tamás Gajda; Glenn Hefter; Ann-Kathrin Leuz; Staffan Sjöberg; Hans Wanner

doi:10.1351/PAC-REP-09-03-05

Publicly Available Published by De Gruyter October 29, 2009

Chemical speciation of environmentally significant metals with inorganic ligands. Part 3: The Pb2+ + OH–, Cl–, CO32–, SO42–, and PO43– systems (IUPAC Technical Report)

Kipton J. Powell , Paul L. Brown , Robert H. Byrne , Tamás Gajda , Glenn Hefter , Ann-Kathrin Leuz , Staffan Sjöberg and Hans Wanner

From the journal Pure and Applied Chemistry

https://doi.org/10.1351/PAC-REP-09-03-05

Abstract

Complex formation between Pb^II and the common environmental inorganic ligands, Cl^–, OH^–, CO₃^2–, SO₄^2–, and PO₄^3–, can be significant in natural waters with low concentrations of organic matter. Numerical modeling of the speciation of Pb^II amongst these inorganic ligands requires reliable values for the relevant stability (formation) constants. This paper provides a critical review of such constants and related thermodynamic data. It recommends values of log₁₀ β_p,q,r° valid at I_m = 0 mol kg^–1 and 25 °C (298.15 K), along with the equations and empirical coefficients required to calculate log₁₀β_p,q,r values at higher ionic strengths using the Brønsted–Guggenheim–Scatchard specific ion interaction theory (SIT). Some values for reaction enthalpies, Δ_rH, are also reported. In weakly acidic fresh water systems (–log₁₀ {[H⁺]/c°} < 6), the speciation of Pb^II is similar to that of Cu^II. In the absence of organic ligands, Pb^II speciation is dominated by Pb²⁺(aq), with PbSO₄(aq) as a minor species. In weakly alkaline solutions, 8.0 < –log₁₀ {[H⁺]/c°} < 9.0, the speciation is dominated by the carbonato species PbCO₃(aq) and Pb(CO₃)₂^2–. In weakly acidic saline systems (–log₁₀ {[H⁺]/c°} < 6), the speciation is dominated by PbCl_n^(2–ⁿ⁾⁺ complexes, (n = 0–3), with Pb²⁺(aq) as a minor species. In this medium (and in seawater), the speciation contrasts with that of Cu^II because of the higher stability of the Pb²⁺-chlorido- complexes. In seawater at –log₁₀ {[H⁺]/c°} = 8.2, the calculated speciation is less well defined, although it is clearly dominated by the uncharged species PbCO₃(aq) (41 % of [Pb]_T) with a significant contribution (16 %) from Pb(CO₃)Cl^– and minor contributions (5–10 %) from PbCl_n^(2–ⁿ⁾⁺, (n = 0–3) and Pb(CO₃)₂^2–. The uncertainty in calculations of Pb^II speciation in seawater arises from (a) the large uncertainty in the stability constant for the apparently dominant species PbCO₃(aq), (b) the reliance on statistical predictions for stability constants of the ternary species Pb(CO₃)Cl^– and Pb(CO₃)OH^–, and (c) the uncertainty in the stability constant for PbCl₄^2–, the available value being considered "indicative" only. There is scope for additional detailed high-quality measurements in the Pb²⁺ + CO₃^2– + Cl^– system.

Keywords: chemical speciation; environmental; lead; ligands; stability constants

Project Year: 1999, Project Code: 1999-050-1-500

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Published Online: 2009-10-29

Published in Print: 2009-10-31

Chemical speciation of environmentally significant metals with inorganic ligands. Part 3: The Pb2+ + OH–, Cl–, CO32–, SO42–, and PO43– systems (IUPAC Technical Report)

Abstract

References

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